Method for the control of undesirable plant growth



United States Patent 3,295,949 METHOD FOR THE CONTROL OF UNDESIRABLE PLANT GROWTH Bryant Leonidas Walworth, Pennington, N.J., assignor to American Cyanamid Company, Stamford, Conn-, a corporation of Maine No Drawing. Original application Sept. 27, 1963, Ser. No. 311,947. Divided and this application Sept. 2, 1965, Ser. No. 484,742

8 Claims. (Cl. 712.7)

This application is a divisional application of application Serial No. 311,947, filed September 27, 1963, now abandoned.

This invention relates to a method for the control of undesirable plant growth. More particularly, it relates to a specific compound and the salts thereof which exhibits both pre-emergence and post-emergence herbicidal activity.

. The successful cultivation of crops normally requires the control of undesirable vegetation with a minimum expenditure of time, effort and expense. Among the methods employed to control such vegetation is the use of herbicidal compositions. While numerous such compositions have been used successfully in the past, none are available which may be applied satisfactorily under a variety of conditions and for a large variety of purposes. Thus, of the compounds useful in the control of undesirable growth, many are extremely selective, i.e., effective against a limited number of plant species. Few are sulficiently water soluble to permit the preparation of simple dilutions in water, while others may be applied only preemergence or post-emergence. Further, most highly effective herbicidal compositions exhibit long-term residual herbicidal activity which prevents their application just prior to planting.

Therefore, it is an object of this invention to provide a method for the control of undesirable plant growth which employs a herbicidal composition which is effective under a variety of conditions, i.e., pre-emergence, postemergence, application to the locus, application to foliage or leaves; and for a large variety of purposes, that is, the control of a wide variety of plan-t species.

A further object of the present invention is to provide aqueous com-positions for the control of undesirable plant growth which are readily prepared by simple dilution in water of highly effective herbicidal compounds.

Another object of this invention is to provide a herbicidal composition having a limited period of residual activity, thus enabling them to be employed shortly before planting.

These and other objects and advantages of the present invention will become more apparent from the detailed description thereof set forth hereinbelow.

According to the present invention, a method is provided for controlling the growth of undesirable plants, plant life or vegetation which comprises applying to the vegetation or to the locus containing the seeds of vegetation or undesirable plant species a herbicidally effective amount of 3-amino-3-carboxypropyl methyl sulfoxirnine and the salts thereof.

Among the salts contemplated are the sulfate, nitrate, halide, such as the chloride, phosphate, acetate, propionate, butyrate, gulconate, ammonia, dimethylamine, diethylamine, alkanolamine such as ethanolamine, alkali metal salts such as the sodium or potassium salts and the alkaline earth metal salts such as calcium and magnesium salts. These salts and their equivalents may be prepared by conventional procedures as by introducing the sulfoximine into an aqueous medium and reacting it with the appropriate inorganic, organic, acid amine, alkali metal or alkaline earth metal base. prepared as follows:

PREPARATION OF SULFOXIMINE SALTS 3-AMINO-3-CARBOXYPROPYL METHYL SULFOXIMINE HYDROGEN SULFATE Illustratively, they may be To 18 grams of methionine sulfoximine (0.1 mole) in 50 ml. of water is slowly added 10 ml. of concentrated sulfuric acid with stirring. The mixture is cooled to 0-5 C. and ethanol added to precipitate the crude 3-amino-3- carboxypropyl methyl sulfoximine hydrogen sulfate. This is recrystallized from water-ethanol mixtures to melting point -192 C.

3-AMINO-3-CARBOXYPROPYL METHYL SULFOXIMINE DIHYDROGEN PHOSPHATE To 50 cc. of 10% phosphoric acid, is added 9.0 grams of methionine sulfoximine. The solution is concentrated under vacuum at 35 C. until a precipitate is observed; crystallization is completed by cooling to 5 C. The product is collected by filtration.

3-AMINO-3-CARBOXYPROPYL METHYL SULFOXIMINE HYDROCHLORIDE 3-amino-3-carboxypropyl methyl sulfoximine gulconate 3-amino-3-carboxypropyl methyl sulfoximine picrate The herbicidal compositions usable in the process of this invention may be prepared by admixing the active 3-amino-3-carboxypropyl methyl sulfoximine compound, including salts thereof, with any of the inert liquid or solid carriers generally employed in the preparation of .agricultural sprays, dusts or Wettable powder formulations.

Liquid formulations may be-prepared by dissolving the active compound in water and, if desired to increase active content of a composition, adding thereto from about 0.1 to 2% of a suitable surface active agent or emulsifying agent.

Dry formulations may be prepared by admixing the active component with an inert solid carrier such as Attaclay, diatomaceous earth, talc, pumice, kaolin, fullers earth, chalk, wood flour, silica, charcoal, activated carbon or other inert powders. In such formulations, approximately 50 to 98% by weight of the composition is. in the form of the inert carrier.

Wettable powder compositions may be prepared by blending an inert solid carrier such as those referred to above and in particular Attaclay with an amount of a suitable emulsifying agent. The active compounds con-. taining Wettable carrier are then dispersed in appropriate quantities of water to provide the proper concentration of active ingredient for the proposed end use.

The compositions of this invention, when used for post-emergence control of undesirable perennial vegetation, is employed in amounts of at least 5 pounds per acre of active compound. For post-emergence control of undesirable annuals, at least /1 pound of active ingredient per acre is desirable; and for pro-emergence control of annuals and perennials a minimum of about 10 pounds per acre of active compound is desirable.

Although the compounds of the instant invention have demonstrated a high order of activity when applied properly as stated above, they have also demonstrated shortterm residual activity. This feature contributes significantly to'the usefulness of the compounds in that it permits herbicidal application to a locus just prior to planting. It will also be noted that the compounds of this invention when applied to the foliage of certain perennials are translocated through the foliage into the buds or to the root parts of the plant, thereby inhibiting or preventing the regrowth of such plant parts.

In order that the present invention may be more clearly understood, the following examples are given primarily -by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

Example 1 Effectiveness of the 3-amino-3-carboxypropyl methyl sulfoxamine hydrogen sulfate as a broad-spectrum or selective post-emergence herbicide is clearly demon- 20 4 ness is rated according to the herbicide activity index set forth hereinbelow.

Herbicide Activity Index TABLE I.BROAD-SPECTRUM HERBIOIDAL ACTIVITY OF 3-AMINO-3-OARBOXY PROPYL METHYL SULFOXIMINE HYDROGEN SULFATE Herbicide Activity, Rate Herbicide Activity; Rate (lb/acre.) (lb. acre.) Test Species Test Species Broccoli 5 *5 5 5 2 Cauliflowen- 5 *5 5 5 Chard, Swiss 5 5- "5 Collards 5 *5 *5- Mallow, Indian. 5

1ax 5- *5- *5- Ragweed, Common.

Mustard- *5 *5 Pea 5- *5- *5- Pepper 5 5 5 Radish 5 5 *5 Sugarbeet 5 5 5- Tomato 5 5 *5 Dmts Trefoil, Birdsfoot b 5- 5- *s Bindweed, Field R 5 R5 R5 Chickweed, Common 5 5- *5 Pigweed 5 5- 5 Purslane 5 5 5- Knotweed 5 3 Alialfa 5- *4+ *3+ Lambs-qnarters *5 *3+ *3+ Cotton 5 5- *4 Spnrge, Spotted 5 Clover, Red. 5- *5- 3+ Celery *2 *1 *1 5- *5- 3+ Clover, White b 3 1 5 5 Clover, Sweet b 0+ 0 0 5 5- Parsnip 1 0 0 5- *4+ *3+ 5 *5- *4+ Wild 0ats 3 0 0 5-- 2 3-3- 0 5- *l 3 0 0 Grabg'r 5 5- 4 0 0 Foxtail, Giant dz Green b 5- *5- *3+ Bentgrass 4 0 0 Monocots Corn 5- *3 *3 Fescue, Creeping. 4 0+ Bluegrass, Ky- 5 3+ *1-3 Ryegrass 3 0 Feseue, Pennlawn- 4+ *1 *0+ Leek *0 *0 *0 Nutsedge, Purple 4+ 0 0 Barnyard Grass 0 0 0 Cheatgrass 4+ Foxtail, Green 0 0 Quackgrass 5 0 Johnson Grass 6 5 *0.1% of sodium salt of Z-ethyl hexyl sulfosuccinate Wetting agent added to the spray solution. "These were established plants of mouse-ear chiekweed and control at 5 lbJacre. without subsequent regrowth, demonstrates systemic activity on a dicotyledon plant species.

strated by the results of the following tests wherein healthy monocotyledon and dicotyledon plants, approximately two weeks old, are treated with solutions containing graded levels of active ingredient.

In these tests dicotyledon species and 22 monocotyledon species growing in small containers are sprayed to the point of runoff with water solutions containing 3- amino-3-carboxypropyl methyl sulfoxirnine hydrogen sulfate in quantities determined to produce treatments equivalent to /2, 1 and 5 pounds of herbicide active ingredient per acre.

After treatment the plants are placed in a greenhouse and cared for in the usual manner. Three weeks after treatment the tests are terminated. All plants are examined 3 weeks after treatment and the results recorded.

These results appear in Table I below where eifective- Example 2 The unusual foliar systemic activity which the compounds of the instant invention exhibit with respect to certain perennial plants is demonstrated by the following tests where established Johnson grass and quackgrass plants, in 1 quart glazed crocks, were sprayed at 86 gal. of H 0 per acre with aqueous solutions of 3-amino-3- carboxypropyl methyl sulfoximine hydrogen sulfate containing 0.1%, by weight, of sodium dicotylsulfosnccinate. Rates of foliar application were equivalent to 2.5, 5, 10 and 20 pounds of active ingredient per acre. Ten weeks after application no regrowth from underground plant parts had occurred. While Canada thistle and purple nutsedge were treated in the same manner and the foliage killed, some regrowth eventually occurred. In another TABLE IL-HERBICIDAL ACTIVITY Eatample 4 Q In the following test, barley, oats, winter rye, wheat, crabgrass, alfalfa, wild oats and corn were planted in separate jiffy flats, On the sixth, eighth, eleventh, fifteenth and twenty-second day after planting, two sets [Rate of application-psternergence (lbJa ere. in 86 gal. of spray/acre.)]

Test Species 20 10 2. 5

Experiment 1, non-replicated:

Johnson grass- 3-week data 5 4 5 1 -week data D5 R4 D5 1 Quackgrass- 3-week data T5 T5 5- 1 10-week data D+5 D5 R5- 1 Canada thistle- 3-week data R5 R5 10-week data R5 R5 Purple nutsedge- 3-week data- G133 G132 10-week data" R3 R2 Experiment 2, triplicat 3-week data:

Johnson grass 3, 5, 5 5, 5, 5- 5, 5-, 5- 1, 5, l Quackgrass 5, 5, 5- 5,5,5 5,5,3 1,2,1

Example 3 of separate flats, twice replicated and containing the above-identified plant species were sprayed with (1) an To demonstrate the effectiveness of the compounds of F P solmon of 3ammo'3'carboxypmpyl methyl P this invention as pre-emergence herbicides, suflicient quanfoxlmm? hydrogen Sulfate and (2) an Q Q solutlon titles of 3-amino-3-carboxypropyl methyl sulfoximine hyof f j? YP P mePhyl sulfoxlfmne hydrogen drogen sulfate were dissolved in water to provide the su1fate contammg Welght, of dloctylsul' desired concentration of ingredient in solution. Halffosuccmate- P apPhcatlons were equlv'alent to 6 pint quantities of potting soil are separately seeded to a Pounds of acme mgredlent F acrevariety of monoand dicotyledonous plant species. These Thfee Weeks after sp'ray,mg each trcate (1 seed-soil mixtures are then added to seperate one-pint 'j f aI.1d rated according to h herblcldal actwlty cups containing about one inch of potting soil. In one Index glven Example series, each cup is wet with twenty-five milliliters of tap From 92 glven m Table IV below 1t fq water and then with twenty-five milliliters of the herbicidal that j afidltlon of a f 'f to the aqueous her b1c1da1 solution being tested. The treatments are equivalent to P W lncreasfis i ,actlvlty thereof? There 13 also 2, 10 and 50 pounds of active ingredient per acre 40 limited data WhlCh indicate that certain monocots may When the herbicidal solution is added to the various become more Sensmve seeded containers, the containers are placed on green- TABLE IV.P0ST-g% I%IItF(BlENCE @CTIVITY WITH PLANTS house benches and attended to in the conventional manner. EREN AGES Ina second series, the potting soils are prepared and 61b A treated with test solutions in the same manner as described m above. However, no seeds are introduced into these soils until seven days after treatment with the test Test Spams Tune ofApphcatmn (days after seedmg) solutions. 6 8 n 15 22 The first series of seeded pots in this pre-emergence test are examined three weeks after treatment, the second 7 series is examined three weeks after seeding. 0 0 3+ 3 The findings are recorded and appear in Table III 0 0 4 3 below. From this table it is evident that the compounds 0 0 3+ 4 of the instant invention have short-term residual activity, 0 0 4 5- and where application is pre-emergence 10 pounds of ac- U 0 U 3 tive ingredient per acre was an effective control. 0 3 3 3 0 0 0 3 TABLE IIL-PRE-EMERGENCE AND RESIDUAL HERBICI- 0 3 3 3 DAL ACTIVITY 0 0 0 4 0 4+ 5- 5 Seeded Immediately Seeded after 7 days Rate (ill/Acre) 5- 4 0 0 Test Species 5- 5- 3+ 0 5o 10 2 10 2 4+ 0 3+ 5 Bentgrass 5 1 0 3 0 0 0 0 0 3 Bluegrass, Ky- 5- 5 0 3 0 0 5 5 5 1 0 5 0 o 5 2 0 3 0 0 5 5 0 3+ 0 0 =No wetting agent added to the spray solution. 5-- 1 0 3 0 0 +=0.1% of the sodium salt of dioetyl sulfosuceinate added to the spray 5 5 0 5 0 0 solution. 5 5 0 5 0 0 g g 8 g g g 7 Example 5 5 5 2 5 5 0 5 g i g g Followlng the procedure of Example 1, an aqueous g 0 0 5 O 0 solution of 3-amino-3carboxypropyl methyl sulfoximine 5 5 0 5 0 0 as the free base was applied post-emergence at the rate of 12.5 lbs. of active material per acre to healthy two- Week-old bindweed, Canada thistle, Johnson grass, nutsedge, quackgrass, lambs quarters, mustard, pigWeed, harley, crabgrass, wild oats, tomato, radish and wheat plants.

The thus-treated plants were placed in a greenhouse and cared for in the usual manner until the tests were terminated three weeks after treatment.

At the end of three weeks, the plants were examined and rated according to the Herbicide Activity Index described in Example 1. All plants were rated (all foliage killed) excepting nutsedge which was rated 3 (severe injury),

Example 6 Following the procedure of Example 3, 3-amino-3- carboxypropyl methyl sulfoximine as the free base was applied pre-emergence at the rate of 25 pounds per acre to potted seeds of millet, mustard, radish and wheat.

At the termination of the test period, the seeded containers were examined and rated according to the herlaicide activity index. Millet was rated 5, rnustard and radish 5-, and wheat rated trace (T).

Example 7 The sulfate, potassium and dimethylarnine salts of 3-arnino-3 carboxypropyl methyl sufoximine were tested for post-emergence activity against mustard, pigweed, crabg-rass, radish and tomato.

Treatments 'Were at the rate of 0.5 pound per acre.

All salts received a 5 rating against mustard and radish; all received a 5 rating again pigweed; the sulfate and potassium salts were rated 4 against crabgrass; the dimethy'lamine salt rated 3 against crabgrass; and the sulfate rated 5 against tomato, while the potassium salt and dime-thylamine salt rated 1 and 3, respectively, against tomato.

In Example 7 above, the potassium salt reported was prepared by dissolving one mole of 3-amino-3-car boxypropyl methyl sulfoximine hydrogen sulfate in an aqe'ous solution containing 1.5 moles of potassium hydroxide. The dimethy-lamine salt was prepared in a similar fashion employing 2 moles of dimethylamine. U

The herbicidal activity of 3- amino-3-carboxypropyl methyl sulfoximine as the free base or as various salts illustrated above is believed to be unique. This is thought to *be demonstrated by the fact that 3-amino-3-carboxypropyl ethyl sulfoximine, the next higher homologue, was determined to he herbicidal'ly inactive. This was determined in postand pre-emergence tests which employed the ethyl-homologue at rates of 10 and 25 pounds per acre, respectively. The post-emergence tests were conplants which comprises applying to the foliage thereof a herbi-oid ally effective amount of 3-amino-3-carb-oxypropy'l methyl sulfoxi-mine and its 'herbicidally effective salts.

2. A method according to claim 1 in which the undesirable plants are perennials and the herbicidally effective amount is at the rate of at least about 5 pounds per acre.

3. A method according to claim 1 in which the undesirable plants are annuals and the herbicidally effective amount is at least about A pound per acre.

4. A method according to claim 1 in which the com- -pound is 3-amin-o-3 carboxypropyl methyl sulfoximine hydrogen sulfate.

5. A method forthe pre-emergence control of undesirable plant growth which comprises applying to an area to be protected from such growth a herbicidally effective amount of 3-amino-3-carboxypropyl methyl sulfoximine and its herbicidally effective salts.

6. A method according to claim 5 wherein the amount of compound employed is at least about 10 pounds per acre.

7. A method for controlling undesirable perennial grasses which comprises applying to the grasses a herbicidally effective amount of the herbicidally effective inorganic acid salts of 3-arnino-3 carboxypropyl methyl sulfoximine.

8. A method according to claim 7 in 'which the compound applied is 3-amino-3-carboxypropyl methyl sulfoximine hydrogen sulfate.

References Cited by the Examiner UNITED STATES PATENTS 4/ 1965- Husted 71-2.7

OTHER REFERENCES Chemical Abstracts, vol. 53, column 15236(a), and Subject Index, page 2721*(S), 1959.

LEWIS GO'ITS, Primaly Examiner.

JAMES O. THOMAS, Examiner.

ELBERT L. ROBERTS, Assistant Examiner. 

1. A METHOD FOR CONTROLLING THE GROWTH OF UNDESIRABLE PLANTS WHICH COMPRISES APPLYING TO THE FOLIAGE THEREOF A HERBICIDALLY EFFECTIVE AMOUNT OF 3-AMINO-3-CARBOXYPROPYL METHYL SULFOXIMIME AND ITS HERBICIDALLY EFFECTIVE SALTS. 